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The Metallic State Of Conducting Polymers: Microwave Dielectric Response And Optical Conductivity

A. J. Epstein, J. Joo, R. S. Kohlman, A. G. Macdiarmid, J. M. Weisinger, Y. Min, J. P. Pouget, J. Tsukamoto

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ABSTRACTRecent advances in processing of polyaniline and polyacetylene have resulted in a new generation of conducting polymers with higher dc conductivities. We present the temperature (T) dependent microwave frequency dielectric constant, dc conductivity, and Kramers-Kronig analysis of conducting polyaniline and polyacetylene. The low temperature dielectric constant, ε, increases with the square of the x-ray crystalline domain length for preparations of HCl protonated polyaniline. For the highest crystalline polyaniline samples, ε increases dramatically with increasing T, supporting formation of three-dimensional (3-D) coupled “mesoscopic” Metallic regions. A “metallic” negative ε is observed for d,1-camphor sulfonie acid doped polyaniline prepared in m-cresol. Optical studies show a linear increase in reflectivity below 7000 cm-1. Below 600 cm-1 the reflectance increases rapidly. Kramers-Kronig analysis of the ir-visible results are presented. Highly conducting polyaniline is shown to have two plasma frequencies, one at ∼ 1.1 eV involving all the conduction band electrons, and one at ∼0.015 eV (120 cm-1) that is suggested to arise from the most delocalized electrons. The concept of inhomogeneous disorder is introduced. The results for polyaniline are compared to those of highly doped polyacetylene which also show metallic negative ε demonstrating the intrinsic metallic nature of the new generation of conducting polymers.